Method of forming a catalyst with inhibited mobility of nano-active material

ABSTRACT

A method of forming a catalyst, comprising: providing a plurality of support particles and a plurality of mobility-inhibiting particles, wherein each support particle in the plurality of support particles is bonded with its own catalytic particle; and bonding the plurality of mobility-inhibiting particles to the plurality of support particles, wherein each support particle is separated from every other support particle in the plurality of support particles by at least one of the mobility-inhibiting particles, and wherein the mobility-inhibiting particles are configured to prevent the catalytic particles from moving from one support particle to another support particle.

CROSS-REFERENCE TO RELATED APPLICATIONS:

This application is a continuation of U.S. patent application Ser. No.12/962,508, filed Dec. 7, 2010 which claims priority to U.S. ProvisionalPatent Application Ser. No. 61/284,329, filed Dec. 15, 2009 and entitled“MATERIALS PROCESSING”, all of which are hereby incorporated herein byreference in their entirety as if set forth herein.

FIELD OF THE INVENTION

The present invention relates to the field of catalysts. Morespecifically, the present invention relates to a method of formingcatalysts where the mobility of the active catalytic particles isinhibited.

BACKGROUND OF THE INVENTION

Catalysts are used to facilitate and speed up reactions. In someapplications, it is desirable to utilize small-scale catalyst material,such as catalytic nano-sized particles. Furthermore, it is alsooftentimes desirable to use support structures to provide a substructureupon which the catalytic particles can reside.

In FIG. 1A, catalyst 100 comprises a plurality of support particles 110a-d, each having at least one corresponding catalytic particle 120 a-d.Although FIGS. 1A-C show only four support particles 110, it iscontemplated that the catalyst 100 can comprise any number of supportparticles 110. The catalytic particles 120 a-d can be chemicallyabsorbed or bonded onto the surface of the support particles 110 a-d.However, the catalytic particles 120 a-d are not permanently fixed totheir bonded support particles 110 a-d. Rather, they are able to movefrom one support particle 110 to another. For example, FIGS. 1A-B showcatalytic particles 120 b and 120 c moving from their respective supportparticles 110 b and 110 c to adjacent support particles 110 a and 110 d,respectively, such that catalytic particles 120 a and 120 b are disposedon support particle 110 a and catalytic particles 120 c and 120 d aredisposed on support particle 110 d. In high temperature applications,the movement of these catalytic particles is magnified. As seen in FIG.1C, as catalytic particles 120 b and 120 c move to neighboring supportparticles 110 a and 110 d, they begin to coalesce with other catalyticparticles 120 a and 120 d on those neighboring support particles,resulting in larger catalytic particles 120 ab and 120 cd.

It is understood that the effectiveness and activity of a catalyst aredirectly proportional to the size of the catalytic particles on thesurface of the support particles. As the catalytic particles coalesceinto larger clumps, the catalytic particle sizes increase, the surfacearea of the catalytic particles decreases, and the effectiveness of thecatalyst is detrimentally affected.

SUMMARY OF THE INVENTION

The present invention inhibits this movement of catalytic particles andreduces their coalescence, thereby minimizing their individual size andmaximizing their combined surface area. The present invention achievesthese results by providing one or more mobility-inhibiting particlesbetween the support particles in order to prevent the catalyticparticles from moving from one support particles to another.

In one aspect of the present invention, a method of forming a catalystis provided. The method comprises providing a plurality of supportparticles and a plurality of mobility-inhibiting particles. Each supportparticle in the plurality of support particles is bonded with its owncatalytic particle. The plurality of mobility-inhibiting particles isthen bonded to the plurality of support particles. Each support particleis separated from every other support particle in the plurality ofsupport particles by at least one of the mobility-inhibiting particles.The mobility-inhibiting particles are configured to prevent thecatalytic particles from moving from one support particle to anothersupport particle.

In another aspect of the present invention, a method of forming acatalyst is provided. The method comprises providing a plurality ofsupport particles and a plurality of mobility-inhibiting particles. Eachsupport particle in the plurality of support particles is bonded withits own catalytic particle. The plurality of support particles isdispersed in a dispersion liquid, thereby forming a dispersion ofsupport particles. The plurality of mobility-inhibiting particles isdispersed in a dispersion liquid, thereby forming a dispersion ofmobility-inhibiting particles. The dispersion of support particles ismixed with the dispersion of mobility-inhibiting particles, therebyforming a wet mixture. The wet mixture is freeze-dried, thereby forminga dried mixture. The dried mixture is then calcined, thereby forming acluster of the plurality of support particles and the plurality ofmobility-inhibiting particles. Each support particle is separated fromevery other support particle in the plurality of support particles by atleast one of the mobility-inhibiting particles. The mobility-inhibitingparticles are configured to prevent the catalytic particles from movingfrom one support particle to another support particle.

In yet another aspect of the present invention, a catalyst is provided.The catalyst comprises a plurality of support particles. Each supportparticle in the plurality of support particles is bonded with its owncatalytic particle. The catalyst also comprises a plurality ofmobility-inhibiting particles bonded to the plurality of supportparticles. Each support particle is separated from every other supportparticle in the plurality of support particles by at least one of themobility-inhibiting particles. The mobility-inhibiting particles areconfigured to prevent the catalytic particles from moving from onesupport particle to another support particle.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-C illustrate one embodiment of a catalyst susceptible to themovement and coalescence of its catalytic particles.

FIG. 2 is a flow chart illustrating one embodiment of a method offorming a catalyst in accordance with the principles of the presentinvention.

FIG. 3 illustrates one embodiment of a particle production system inaccordance with the principles of the present invention.

FIG. 4 illustrates another embodiment of a particle production system inaccordance with the principles of the present invention.

FIG. 5A illustrates one embodiment of a plurality of support particleswith their associated catalytic particles in accordance with theprinciples of the present invention.

FIG. 5B illustrates one embodiment of a plurality of mobility-inhibitingparticles in accordance with the principles of the present invention.

FIG. 6A illustrates one embodiment of a dispersion of support particleswith their associated catalytic particles in accordance with theprinciples of the present invention.

FIG. 6B illustrates one embodiment of a dispersion ofmobility-inhibiting particles in accordance with the principles of thepresent invention.

FIG. 7 illustrates one embodiment of a mixture of the dispersion ofsupport/catalytic particles of FIG. 6A and the dispersion ofmobility-inhibiting particles of FIG. 6B in accordance with theprinciples of the present invention.

FIG. 8 illustrates one embodiment of a cluster of mobility-inhibitingparticles bonded between support/catalytic particles in accordance withthe principles of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The following description is presented to enable one of ordinary skillin the art to make and use the invention and is provided in the contextof a patent application and its requirements. Various modifications tothe described embodiments will be readily apparent to those skilled inthe art and the generic principles herein may be applied to otherembodiments. Thus, the present invention is not intended to be limitedto the embodiment shown but is to be accorded the widest scopeconsistent with the principles and features described herein.

This disclosure refers to both particles and powders. These two termsare equivalent, except for the caveat that a singular “powder” refers toa collection of particles. The present invention may apply to a widevariety of powders and particles. Powders that fall within the scope ofthe present invention may include, but are not limited to, any of thefollowing: (a) nano-structured powders(nano-powders), having an averagegrain size less than 250 nanometers and an aspect ratio between one andone million; (b) submicron powders, having an average grain size lessthan 1 micron and an aspect ratio between one and one million; (c)ultra-fine powders, having an average grain size less than 100 micronsand an aspect ratio between one and one million; and (d) fine powders,having an average grain size less than 500 microns and an aspect ratiobetween one and one million.

FIG. 2 is a flow chart illustrating one embodiment of a method 200 offorming a catalyst in accordance with the principles of the presentinvention.

At step 210, a plurality of support particles and mobility-inhibitingparticles are provided. Preferably, each support particle is bonded withits own distinct catalytic particle (i.e., a one-to-one ratio betweenthe support particles and the catalytic particles). However, it iscontemplated that some support particles can be free of any catalyticparticles. The term “support/catalytic particle” is used in thisdisclosure to refer to a support particle and the catalytic particlebonded to it. The mobility-inhibiting particles are configured toprevent the catalytic particles from moving from one support particle toanother support particle. In a preferred embodiment, themobility-inhibiting particles comprise one or more materials that thecatalytic particles do not like to travel to or on, thereby reducing themobility of the catalytic particles.

In a preferred embodiment, the support particles have a non-catalyticcomposition, in contrast to the catalytic particles. In this respect,the support particles ideally have a different chemical composition thanthat of the catalytic particles. Similarly, the mobility-inhibitingparticles preferably have a non-catalytic chemical composition that isdifferent from that of both the support particles and the catalyticparticles. However, it is contemplated that the particle chemicalcompositions can vary from embodiment to embodiment. In an exemplaryembodiment, the support particles comprise or consist of aluminum oxideand the catalytic particles comprise or consist of a platinum groupmetal, such as platinum, ruthenium, rhodium, palladium, osmium, oriridium. In some embodiments, the mobility-inhibiting particles compriseor consist of a metal oxide (preferably, a transition metal oxide),including, but not limited to, cerium oxide, lanthanum oxide, andtitanium oxide. In other embodiments, the mobility-inhibiting particlescomprise or consist of a glass or a ceramic, including, but not limitedto, boron nitride, titanium carbide, and titanium diboride. Preferably,the mobility-inhibiting particles do not comprise any precious metals.

In a preferred embodiment, the support particles, the catalystparticles, and the mobility-inhibiting particles are nano-particles.Preferably, the support particles and the mobility-inhibiting particleshave a maximum diameter of 500 nanometers and a minimum diameter of 1-5nanometers, while the catalyst particles have a diameter in the range of0.5-5 nanometers. In some embodiments, the diameter of the supportparticles and the mobility-inhibiting particles is in the range of 10-15nanometers and the diameter of the catalyst particles is in the range of2-5 nanometers. However, it is contemplated that other particle sizescan be employed.

It is contemplated that the nano-scale structure of the particles can beachieved in a variety of ways. In a preferred embodiment, the supportparticles and the catalytic particles are vaporized in the hottestregion of a plasma gun. The vaporized particles are then subjected torapid quenching, causing them to condense. As a result of thisvaporization and condensation, nano-sized support particles are formedwith nano-sized catalytic particles bonded to them.

Examples of particle production systems employing plasma reactors toproduce nano-sized particles are disclosed in U.S. patent applicationSer. No. 12/151,935, filed on May 8, 2008 and entitled, “HIGHLYTURBULENT QUENCH CHAMBER”, the entirety of which is hereby incorporatedby reference as if set forth herein. One such particle production system300 is presented in FIG. 3. The system 300 comprises a precursor supplydevice 310 and a working gas supply device 320 both fluidly coupled to aplasma production chamber 330 having an energy delivery zone 335 formedtherein. The plasma production chamber 330 is fluidly coupled with aninjection port 340 of a constricting quench chamber 345, therebyallowing the energy delivery zone 335 to fluidly communicate with thequench chamber 345. One or more ports 390 also allow fluid communicationof the quench chamber 345 with a controlled atmosphere system 370(indicated by the dotted lines). The quench chamber 345 is also fluidlycoupled with an ejection port 365.

Generally, the plasma production chamber 330 operates as a reactor,producing an output comprising particles within a gas stream. Particleproduction includes the steps of combination, reaction, andconditioning. Working gas is supplied from a gas source to a plasmareactor. Within the plasma reactor, energy is delivered to the workinggas, thereby creating a plasma. A variety of different means can beemployed to deliver this energy, including, but not limited to, DCcoupling, capacitive coupling, inductive coupling, and resonantcoupling. One or more material dispensing devices introduce at least onematerial, preferably in powder form, into the plasma reactor. Thecombination within the plasma reactor of the plasma and the material(s)introduced by the material dispensing device(s) forms a highly reactiveand energetic mixture, wherein the powder can be vaporized. This mixtureof vaporized powder moves through the plasma reactor in the flowdirection of the working gas. As it moves, the mixture cools andparticles are formed therein. The still-energetic output mixture,comprising hot gas and energetic particles, is emitted from the plasmareactor.

In an exemplary embodiment, the plasma production chamber 330 combinesprecursor material (preferably in powder form) supplied from theprecursor supply device 310 and working gas supplied from the workinggas supply device 320 within the energy delivery zone 335, where theworking gas is energized to form a plasma. The plasma is applied to theprecursor material within the energy delivery zone 335 to form anenergized, reactive mixture. This mixture comprises one or morematerials in at least one of a plurality of phases, which may includevapor, gas, and plasma.

The reactive mixture flows from the energy delivery zone 335 into theconstricting quench chamber 345 through the injection port 340. As thehot mixture moves from the energy delivery zone 335, it expands rapidlywithin the quench chamber 345 and cools. While the mixture flows intothe quench chamber 345, the ports 390 supply conditioning fluid alongthe inner surfaces of the quench chamber 345. The conditioning fluidcombines, at least to some extent, with the mixture, and flows from thequench chamber 345 through the ejection port 365.

During a period immediately after entering the quench chamber 345,particle formation occurs. Furthermore, the supply of conditioning fluidalong the inner surfaces of the quench chamber 345 works to conditionthe reactive mixture, to maintain entrainment of the particles therein,and to prevent the depositing of material on the inner surfaces of thequench chamber 345.

Still referring to FIG. 3, the structure of the quench chamber 345 canbe formed of relatively thin walled components capable of dissipatingsubstantial heat. For example, the thin-walled components can conductheat from inside the chamber and radiate the heat to the ambient. Thequench chamber 345 comprises a substantially cylindrical surface 350, acone-like (frusto-conical) surface 355, and an annular surface 360connecting the injection port 340 with the cylindrical surface 350. Thecylindrical surface 350, having a large diameter relative to the size ofthe injection port 340, provides accommodation for the expansion of thereactive mixture that occurs after the mixture flows into the quenchchamber 345. The cone-like surface 355 extends from the cylindricalsurface 350, away from the injection port 340 and towards the ejectionport 365. The cone-like surface 355 is sufficiently smoothly varying soas to not unduly compress fluid flowing from through the quench chamber345 to the ejection port 365.

Substantial heat is emitted, mostly in the form of radiation, from themixture following its entry into the quench chamber 345. The quenchchamber 345 is preferably designed to dissipate this heat efficiently.For example, the surfaces of the quench chamber 345 are preferablyexposed to a cooling apparatus (not shown).

Still referring to FIG. 3, the controlled atmosphere system 370preferably comprises a chamber 385 into which conditioning fluid isintroduced from a reservoir 375 through a conduit 380. The conditioningfluid preferably comprises argon. However, other inert, relatively heavygases are equally preferred. Furthermore, the preferable mechanism ofproviding the conditioning fluid into the quench chamber 345 is theformation of a pressure differential between the quench chamber 345 andthe outlet 365. Such pressure differential will draw the conditioningfluid into the quench chamber 345 through the ports 390. Other lesspreferred methods of providing the conditioning fluid include, but arenot limited to, forming positive pressure within the chamber 385.

The frusto-conical shape of the quench chamber 345 can provide a modestamount of turbulence within the quench region, thereby promoting themixing of the conditioning fluid with the reactive mixture, andincreasing the quenching rate beyond prior art systems. However, in somesituations, an even greater increase in quenching rate may be desired.Such an increase in quenching rate can be achieved by creating a highlyturbulent flow within a region of a quench chamber where theconditioning fluid is mixed with the reactive mixture.

FIG. 4 illustrates a particle production system 400 with a highlyturbulent quench chamber 445. The system 400 comprises a precursorsupply device 410 a working gas supply device 420 fluidly coupled to aplasma production and reaction chamber 430, similar to plasma productionchamber 330 discussed above with reference to FIG. 3. An energy deliverysystem 425 is also coupled with the plasma production and reactorchamber 430. The plasma production and reactor chamber 430 includes aninjection port 440 that communicates fluidly with the constrictingquench chamber 445. One or more ports 490 can also allow fluidcommunication between the quench chamber 445 and a controlled atmospheresystem 470, similar to controlled atmosphere system 370 in FIG. 3. Thequench chamber 445 is also fluidly coupled to an outlet 465.

Generally, the chamber 430 operates as a reactor, similar to chamber 330in FIG. 3, producing an output comprising particles within a gas stream.Production includes the basic steps of combination, reaction, andconditioning as described later herein. The system combines precursormaterial supplied from the precursor supply device 410 and working gassupplied from the working gas supply device 420 within the energydelivery zone of the chamber 430. The system energizes the working gasin the chamber 430 using energy from the energy supply system 490,thereby forming a plasma. The plasma is applied to the precursormaterial within the chamber 430 to form an energized, reactive mixture.This mixture comprises one or more materials in at least one of aplurality of phases, which may include vapor, gas, and plasma. Thereactive mixture flows from the plasma production and reactor chamber430 into the quench chamber 445 through an injection port 440.

The quench chamber 445 preferably comprises a substantially cylindricalsurface 450, a frusto-conical surface 455, and an annular surface 460connecting the injection port 440 with the cylindrical surface 450. Thefrusto-conical surface 460 narrows to meet the outlet 465. The plasmaproduction and reactor chamber 430 includes an extended portion at theend of which the injection port 440 is disposed. This extended portionshortens the distance between the injection port 440 and the outlet 465,reducing the volume of region in which the reactive mixture and theconditioning fluid will mix, referred to as the quench region. In apreferred embodiment, the injection port 440 is arranged coaxially withthe outlet 465. The center of the injection port is positioned a firstdistance d₁ from the outlet 465. The perimeter of the injection port ispositioned a second distance d₂ from a portion of the frusto-conicalsurface 455. The injection port 440 and the frusto-conical surface 455form the aforementioned quench region therebetween. The space betweenthe perimeter of the injection port 440 and the frusto-conical surface455 forms a gap therebetween that acts as a channel for supplyingconditioning fluid into the quench region. The frusto-conical surface455 acts as a funneling surface, channeling fluid through the gap andinto the quench region.

While the reactive mixture flows into the quench chamber 445, the ports490 supply conditioning fluid into the quench chamber 445. Theconditioning fluid then moves along the frusto-conical surface 455,through the gap between the injection port 440 and the frusto-conicalsurface 455, and into the quench region. In some embodiments, thecontrolled atmosphere system 470 is configured to control the volumeflow rate or mass flow rate of the conditioning fluid supplied to thequench region.

As the reactive mixture moves out of the injection port 440, it expandsand mixes with the conditioning fluid. Preferably, the angle at whichthe conditioning fluid is supplied produces a high degree of turbulenceand promotes mixing with the reactive mixture. This turbulence candepend on many parameters. In a preferred embodiment, one or more ofthese parameters is adjustable to control the level of turbulence. Thesefactors include the flow rates of the conditioning fluid, thetemperature of the frusto-conical surface 455, the angle of thefrusto-conical surface 455 (which affects the angle at which theconditioning fluid is supplied into the quench region), and the size ofthe quench region. For example, the relative positioning of thefrusto-conical surface 455 and the injection port 440 is adjustable,which can be used to adjust the volume of quench region. Theseadjustments can be made in a variety of different ways, using a varietyof different mechanisms, including, but not limited to, automated meansand manual means.

During a brief period immediately after entering the quench chamber 445,particle formation occurs. The degree to which the particles agglomeratedepends on the rate of cooling. The cooling rate depends on theturbulence of the flow within the quench region. Preferably, the systemis adjusted to form a highly turbulent flow, and to form very dispersedparticles. For example, in preferred embodiments, the turbidity of theflow within the quench region is such that the flow has a ReynoldsNumber of at least 1000.

Still referring to FIG. 4, the structure of the quench chamber 445 ispreferably formed of relatively thin walled components capable ofdissipating substantial quantities of heat. For example, the thin-walledcomponents can conduct heat from inside the chamber and radiate the heatto the ambient.

Substantial heat is emitted, mostly in the form of radiation, from thereactive mixture following its entry into the quench chamber 445. Thequench chamber 445 is designed to dissipate this heat efficiently. Thesurfaces of the quench chamber 245 are preferably exposed to a coolingsystem (not shown). In a preferred embodiment, the cooling system isconfigured to control a temperature of the frusto-conical surface 455.

Following injection into the quench region, cooling, and particleformation, the mixture flows from the quench chamber 445 through theoutlet port 465. Suction generated by a generator 495 moves the mixtureand conditioning fluid from the quench region into the conduit 492. Fromthe outlet port 465, the mixture flows along the conduit 492, toward thesuction generator 495. Preferably, the particles are removed from themixture by a collection or sampling system (not shown) prior toencountering the suction generator 495.

Still referring to FIG. 4, the controlled atmosphere system 470comprises a chamber 485, fluidly coupled to the quench region throughport(s) 490, into which conditioning fluid is introduced from areservoir, such as reservoir 375 from FIG. 3, through a conduit 480. Asdescribed above, the conditioning fluid preferably comprises argon.However, other inert, relatively heavy gases are equally preferred.Also, as discussed above, the preferable mechanism of providing theconditioning fluid into the quench chamber 445 is the formation of apressure differential between the quench chamber 445 and the outlet 465.Such pressure differential will draw the conditioning fluid into thequench chamber 445 through the ports 490. Other methods of providing theconditioning fluid include, but are not limited to, forming positivepressure within the chamber 485.

The angle of the frusto-conical surface affects the angle at which theconditioning fluid is supplied into the quench region, which can affectthe level of turbulence in the quench region. The conditioning fluidpreferably flows into the quench region along a plurality of momentumvectors. The greater the degree of the angle between the momentumvectors, the higher the level of turbulence that will be produced. In apreferred embodiment, the high turbulent quench chamber comprises afrusto-conical surface that is configured to funnel at least twoconditioning fluid momentum vectors into the quench region such thatthere is at least a 90 degree angle between the two momentum vectors. Itis contemplated that other angle degree thresholds may be applied aswell. For example, attention may also be paid to the angle formedbetween at least one of the conditioning fluid momentum vectors and themomentum vector of the reactive mixture. In one embodiment of a highlyturbulent quench chamber, a reactive mixture inlet is configured tosupply the reactive mixture into the quench region along a firstmomentum vector, the frusto-conical surface is configured to supply theconditioning fluid to the quench region along a second momentum vector,and the second momentum vector has an oblique angle greater than 20degrees relative to the first momentum vector.

The size of the quench region also affects the level of turbulence inthe quench region. The smaller the quench region, the higher the levelof turbulence that will be produced. The size of the quench region canbe reduced by reducing the distance between the center of the injectionport 440 and the outlet 465.

The high turbulence produced by the embodiments of the present inventiondecreases the period during which particles formed can agglomerate withone another, thereby producing particles of more uniform size, and insome instances, producing smaller-sized particles. Both of thesefeatures lead to particles with increased dispersibility and increasedratio of surface area to volume.

Referring back to the method 200 in FIG. 2, particle production system200 or 300 (or variations thereof) can be used to provide one or more ofthe support particles, catalytic particles, and mobility-inhibitingparticles in nano-scale form. For example, these particles can beintroduced as micron-sized precursor material into the particleproduction system, where they are vaporized and then condensed to formnano-size particles. In a preferred embodiment, the support/catalyticparticles are formed and provided separately from themobility-inhibiting particles, thereby avoiding any prematureinteraction (e.g., bonding) between the mobility-inhibiting particlesand the support/catalytic particles. Such separation can be achieved ina variety of ways, including, but not limited to, using differentparticle production systems for both groups, or by using the sameparticle production system for both groups at different times.

FIG. 5A illustrates one embodiment of a plurality of support particles510 provided in step 210 of method 200. Each support particle 510 has acatalytic particle 520 bonded to it (preferably to its exteriorsurface). Although, in some embodiments, certain support particles 510may be absent a catalytic particle 520. It is contemplated that the sizeof the catalytic particle 520 on the support particle 510 can beaffected by changing the amount of catalytic material provided to theparticle production system or by otherwise adjusting the mix ratio ofcatalytic particles to support particles provided to the particleproduction system. The larger the concentration of catalytic particlesprovided to the particle production system, the larger the size of thecatalytic particles 520 bonded to the support particles 510.

FIG. 5B illustrates one embodiment of a plurality of mobility-inhibitingparticles 530 provided in step 210 of method 200. The stripes on themobility-inhibiting particles 530 are provided solely for the purpose ofhelping to distinguish the mobility-inhibiting particles 530 from thesupport particles 510.

At step 220 of method 200, the support/catalytic particles and themobility-inhibiting particles are dispersed in liquid. FIG. 6Aillustrates one embodiment of a dispersion 625 of support/catalyticparticles. A close-up of the dispersion 625 shows the support/catalyticparticles being separated by a liquid 615 a and being made up of supportparticles 610 having catalytic particles 620 bonded to them. FIG. 6Billustrates one embodiment of a dispersion 635 of mobility-inhibitingparticles 630. A close-up of the dispersion 635 shows themobility-inhibiting particles 630 being separated by a liquid 615 b.Although FIGS. 6A-B show the support/catalytic particles and themobility-inhibiting particles in separate dispersions 625 and 635, it iscontemplated that they can also be dispersed in the same container atthe same time to form one dispersion.

The dispersion liquids 615 a and 615 b can be any liquids configured todisperse the support/catalytic particles and the mobility-inhibitingparticles, respectively. In a preferred embodiment, the dispersionliquids comprise or consist of water or any organic liquid, such asglycol ethers. In some embodiments, dispersions 625 and 635 both use thesame type of dispersion liquid. In other embodiments, dispersions 625and 635 use different types of dispersion liquids (e.g., dispersionliquid 615 a is water and dispersion liquid 615 b is ethylene glycol).

In some embodiments, one or more surfactants or other dispersing aids,such as cationic, anionic, zwitterionic, and/or non-ionic carbon basedoligomers and/or polymers, can be added to the dispersion liquid.Certain surfactants can be added to the dispersion in order to adjustits acidity and make it stable. Acids can be added to the dispersion inorder to acidify the surface of N-oxide particles. The surfactants arecarefully chosen so that they will not be harmful to the catalystmaterial. In preferred embodiments, no sulfates or phosphates are addedto the dispersion. Examples of surfactants that can be added to thedispersion liquid are carboxylic acids, polyamines, and polyethers. Itis contemplated that other surfactants or dispersing aids can be used aswell.

It is contemplated that the different variations of particle, dispersionliquid, and surfactant concentrations can be employed. In a preferredembodiment, the dispersion comprises a 5-25% by weight concentration ofpowder, meaning that the support/catalytic particles and themobility-inhibiting particles each make up approximately 5-25% by weightof their respective dispersions. In a preferred embodiment, thedispersion comprises a 1-10% by weight concentration of surfactant orother dispersing aid. Preferably, the surfactant or other dispersing aidaccounts for approximately 5% or less of the dispersion.

At step 230 of method 200, the dispersed support/catalytic particles andmobility-inhibiting particles are mixed to form a mixture. If thesupport/catalytic particles and the mobility-inhibiting particles werenot originally dispersed together, or not subsequently placed into thesame container to form a single dispersion, then they are at this timeplaced into the same container where they can be mixed together. In apreferred embodiment, the mixing is performed by sonication, mechanicalmixing, and/or shear mixing. However, it is contemplated that a varietyof other agitation methods can be employed in order to perform thismixing.

FIG. 7 illustrates one embodiment of a mixture 745 of the dispersions inone container. The mixture 745 comprises a plurality of supportparticles 710, each having a catalytic particle 720 bonded to it, andmobility-inhibiting particles 730. The particles are separated by theliquid 715, which can comprise any dispersion liquids and surfactants(or other dispersing aids) used in the prior steps.

At step 240, the dispersion liquid is removed from the mixture to form adried mixture. It is contemplated that the liquid can be removed in avariety of ways. In one embodiment, the dispersion of particles isfreeze-dried. The mixture is poured into a freeze-dry appropriatevessel. It is then frozen with liquid nitrogen or some other medium thatis cool enough to freeze the dispersion of particles. In one embodiment,the liquid nitrogen, or other freezing medium, is at approximately −60degrees Celsius. However, it is contemplated that the liquid nitrogen,or other freezing medium, can be used at other temperatures as well. Themixture is then placed into a vacuum system, where the dispersion ofparticles remains frozen as the water, or other dispersing liquid, isremoved via vacuum pressure. In one embodiment, a vacuum pressure ofapproximately 10 microns is employed. In other embodiments, a vacuumpressure of between approximately 2 microns and approximately 5 micronsis employed.

The vacuum pressure removes the water and any other liquid in themixture having a higher vapor pressure than water. However, in someembodiments, the surfactant remains with the frozen dispersion ofparticles. The removal of the water leaves a porous powder structure ofthe support/catalytic particles and the mobility-inhibiting particles,with the surfactant disposed within the pores. The resulting powder isin an intermediate state, being loosely bonded together, yet dry to thetouch, providing mechanical handling ability.

At step 250, the dried mixture is calcined, thereby baking off anysurfactant and forming clusters of mobility-inhibiting particles bondedbetween the support/catalytic particles. In some embodiments, the powderis placed in a crucible. It is contemplated that the crucible can bemade of ceramic or a variety of other materials. The crucible is thenplaced in a calcining furnace, where it is heated at a given temperaturefor a given time. In some embodiments, the crucible is heated in thecalcining furnace at approximately 550 degrees Celsius for approximately2 hours. However, it is contemplated that other temperatures and heatingtime can be employed as well. In some embodiments, the crucible isplaced in a furnace that has already been preheated to the desiredbaking temperature. Test results have shown that by preheating thefurnace before placing the crucible inside, instead of ramping up thetemperature to the desired temperature while the crucible is in thefurnace, the dispersion of the metal particles can be maximized.However, it is contemplated that, in some embodiments, the furnacetemperature can be ramped up while the crucible is in the furnace. Insome embodiments, a ramp rate of 1-50 degrees Celsius is employed toraise the temperature of the furnace while the crucible is inside. In apreferred embodiment, the furnace provides an ambient air environmentwithin which the crucible, and consequently the powder, can be heated.It is contemplated that the environment within the furnace need notcomprise air. However, it preferably contains some amount of oxygen.

The calcining of the dried mixture takes it from a Van der Waals orproximity attraction between the particles to an actual covalent bondbetween the particles, resulting in a surfactant-free agglomeration ofthe support/catalytic particles and the mobility-inhibiting particles.FIG. 8 illustrates one embodiment of a cluster of mobility-inhibitingparticles 830 bonded between support particles 810, which have catalyticparticles 820 bonded to them. In some embodiments, the present inventionproduces clusters in the range of 0.5-50 microns. In some embodiments,the present invention produces clusters in the range of 5-10 microns.However, it is contemplated that other cluster sizes can be produced aswell.

In some embodiments, the loading percentages of the powders (support,catalyst, and mobility-inhibiting) are adjusted in order to achieve adesired powder concentration for each particular type of powder in theresulting clusters. In some embodiments, a 0.01-15% loading of catalystpowder is employed. In a preferred embodiment, a 0.5-3% loading ofcatalyst powder is employed. However, it is contemplated that otherloading percentages can be employed as well.

In a preferred embodiment, the support particles, the catalystparticles, and the mobility-inhibiting particles in the resultingclusters are nano-particles. Preferably, the support particles and themobility-inhibiting particles have a maximum diameter of 500 nanometersand a minimum diameter of between 1-5 nanometers, while the catalystparticles have a diameter in the range of 0.5-5 nanometers. In someembodiments, the diameter of the support particles and themobility-inhibiting particles is in the range of 5-20 nanometers. Insome embodiments, the diameter of the support particles and themobility-inhibiting particles is in the range of 10-15 nanometers andthe diameter of the catalyst particles is in the range of 2-5nanometers. However, it is contemplated that other particle sizes can beemployed.

The introduction and bonding of mobility-inhibiting particles to andbetween the support/catalytic particles prevents the catalytic particlesfrom moving from one support particle to another, thereby preventing thecoalescence of the catalytic particles. As a result, the size of theindividual catalytic particles can be minimized and the total catalyticsurface area of the cluster can be maximized.

The present invention has been described in terms of specificembodiments incorporating details to facilitate the understanding ofprinciples of construction and operation of the invention. Suchreference herein to specific embodiments and details thereof is notintended to limit the scope of the claims appended hereto. It will bereadily apparent to one skilled in the art that other variousmodifications may be made in the embodiment chosen for illustrationwithout departing from the spirit and scope of the invention as definedby the claims.

What is claimed is:
 1. A method of forming a catalyst, comprising:nano-sizing a precursor support powder; nano-sizing a precursorcatalytic powder; and bonding the nano-sized catalytic powder to thenano-sized support powder to form combined support/catalytic particles;and bonding a plurality of mobility-inhibiting particles to the combinedsupport/catalytic particles, wherein the mobility-inhibiting particlesare configured to inhibit movement of the catalytic particles on thesupport particles.
 2. The method of claim 1, wherein the precursorsupport powder has an average grain size equal to or greater than 1micron; and the catalytic powder has an average grain size equal to orgreater than 1 micron.
 3. The method of claim 1, wherein: nano-sizingthe precursor support powder and the precursor catalytic powdercomprises applying a plasma stream to the precursor support powder andto the precursor catalytic powder, thereby vaporizing the precursorsupport powder and the precursor catalytic powder; and bonding thenano-sized catalytic powder to the nano-sized support to form thecombined support/catalytic particles comprises condensing the vaporizedsupport powder and the vaporized catalytic powder to form the combinedsupport/catalytic particles.
 4. The method of claim 1, wherein theplurality of mobility-inhibiting particles are formed by nano-sizing aprecursor mobility-inhibiting powder that has an average grain sizeequal to or greater than 1 micron.
 5. The method of claim 4, whereinnano-sizing the precursor mobility-inhibiting powder comprises: applyinga plasma stream to the precursor mobility-inhibiting powder, therebyvaporizing the precursor mobility-inhibiting powder; and condensing thevaporized mobility-inhibiting powder.
 6. The method of claim 1,comprising: dispersing the support/catalytic particles in a dispersionliquid; dispersing the plurality of mobility-inhibiting particles in adispersion liquid; and mixing the dispersed support/catalytic particlesparticles with the dispersed mobility-inhibiting particles, therebyforming a mixture of the dispersed support/catalytic particles and thedispersed mobility-inhibiting particles.
 7. The method of claim 6,wherein the dispersion liquid for at least one of the support/catalyticparticles and the mobility-inhibiting particles comprises water.
 8. Themethod of claim 6, wherein the dispersion liquid for at least one of thesupport/catalytic particles and the mobility-inhibiting particlescomprises an organic liquid.
 9. The method of claim 8, wherein theorganic liquid is a glycol ether.
 10. The method of claim 6, wherein atleast one of dispersing the plurality of support/catalytic particles anddispersing the plurality of mobility-inhibiting particles comprisesadding a surfactant to the dispersion liquid.
 11. The method of claim10, wherein the surfactant is selected from the group consisting of acarboxylic acid, a polyamine, and a polyether.
 12. The method of claim6, wherein the dispersed support/catalytic particles and the dispersedmobility-inhibiting particles are mixed using a sonication process. 13.The method of claim 6, wherein the step of bonding the plurality ofmobility-inhibiting particles to the support/catalytic particles,comprises freeze-drying the mixture of dispersed support/catalyticsupport particles and dispersed mobility-inhibiting particles, therebyforming a dried mixture of dispersed support/catalytic particles anddispersed mobility-inhibiting particles.
 14. The method of claim 13,wherein the step of bonding plurality of mobility-inhibiting particlesto the support/catalytic particles comprises calcining the dried mixtureof dispersed support/catalytic particles and dispersedmobility-inhibiting particles.
 15. The method of claim 1, wherein thenano-sized support powder comprises alumina.
 16. The method of claim 1,wherein the nano-sized catalytic powder comprises platinum.
 17. Themethod of claim 1, wherein the plurality of mobility-inhibitingparticles comprises a different chemical composition than thesupport/catalytic particles.
 18. The method of claim 17, wherein theplurality of mobility-inhibiting particles comprises a plurality ofceramic particles.
 19. The method of claim 17, wherein the plurality ofmobility-inhibiting particles comprises a plurality of metal-oxideparticles.
 20. The method of claim 1, wherein: the nano-sized supportpowder has a diameter of between 1 nanometer and 500 nanometers; thenano-sized catalytic powder has a diameter between 0.5 nanometers and 5nanometers; and the mobility-inhibiting particles have a diameterbetween 1 nanometer and 500 nanometers.
 21. A method of forming acatalyst, comprising: nano-sizing a precursor support powder;nano-sizing a precursor catalytic powder; and bonding the nano-sizedcatalytic powder to the nano-sized support powder to form combinedsupport/catalytic particles; dispersing the support/catalytic particlesin a dispersion liquid, thereby forming a dispersion ofsupport/catalytic particles; dispersing a plurality ofmobility-inhibiting particles in a dispersion liquid, thereby forming adispersion of mobility-inhibiting particles; mixing the dispersion ofsupport/catalytic particles with the dispersion of mobility-inhibitingparticles, thereby forming a wet mixture; freeze-drying the wet mixture,thereby forming a dried mixture; and calcining the dried mixture,thereby forming a cluster of the support/catalytic particles and theplurality of mobility-inhibiting particles, wherein themobility-inhibiting particles are configured to inhibit movement of thecatalytic particles on the support particles.
 22. The method of claim21, comprising: nano-sizing a precursor support powder that has anaverage grain size equal to or greater than 1 micron; nano-sizing aprecursor catalytic powder that has an average grain size equal to orgreater than 1 micron; and nano-sizing a precursor mobility-inhibitingpowder that has an average grain size equal to or greater than 1 micron.23. The method of claim 21, wherein nano-sizing the precursor powderscomprise: applying a plasma stream to the precursor powders, therebyvaporizing the precursor powders; and condensing the vaporized powders.24. The method of claim 21, wherein the dispersion liquid for at leastone of the support/catalytic particles and the mobility-inhibitingparticles comprises water.
 25. The method of claim 21, wherein thedispersion liquid for at least one of the support/catalytic particlesand the mobility-inhibiting particles comprises an organic liquid. 26.The method of claim 25, wherein the organic liquid is a glycol ether.27. The method of claim 21, wherein at least one of dispersing thesupport/catalytic particles and dispersing the plurality ofmobility-inhibiting particles comprises adding a surfactant to thedispersion liquid.
 28. The method of claim 27, wherein the surfactant isselected from the group consisting of a carboxylic acid, a polyamine,and a polyether.
 29. The method of claim 21, wherein the step of mixingthe dispersion of support/catalytic particles with the dispersion ofmobility-inhibiting particles comprises using a sonication process. 30.The method of claim 21, wherein the nano-sized support powder comprisesalumina.
 31. The method of claim 21, wherein the nano-sized catalyticpowder comprises platinum.
 32. The method of claim 21, wherein theplurality of mobility-inhibiting particles comprises a differentchemical composition than the support/catalytic particles.
 33. Themethod of claim 32, wherein the plurality of mobility-inhibitingparticles comprises a plurality of ceramic particles.
 34. The method ofclaim 32, wherein the plurality of mobility-inhibiting particlescomprises a plurality of metal-oxide particles.
 35. The method of claim21, wherein: nano-sized support powder has a diameter of between 1nanometer and 500 nanometers; the nano-sized catalytic powder has adiameter between 0.5 nanometers and 5 nanometers; and themobility-inhibiting particles have a diameter between 1 nanometer and500 nanometers.
 36. A catalyst comprising: a plurality of supportparticles comprising alumina and having a diameter between 1 nanometerand 500 nanometers, the plurality of support particles are bonded to aplurality catalytic particles to form support/catalytic particles; and aplurality of mobility-inhibiting particles having a diameter between 1nanometer and 500 nanometers bonded to the plurality ofsupport/catalytic particles, wherein the mobility-inhibiting particlesare configured to inhibit the catalytic particles from moving on thesupport particles.
 37. The catalyst of claim 36, wherein the catalyticparticles comprise platinum.
 38. The catalyst of claim 36, wherein theplurality of mobility-inhibiting particles comprises a differentchemical composition than the plurality of support particles.
 39. Thecatalyst of claim 38, wherein the plurality of mobility-inhibitingparticles comprises a plurality of ceramic particles.
 40. The catalystof claim 38, wherein the plurality of mobility-inhibiting particlescomprises a plurality of metal-oxide particles.